WO2018235688A1 - Curable composition, semi-cured product, cured product, optical member, lens and compound - Google Patents

Abstract

The present invention addresses the problem of developing: a compound which enables the achievement of an optical member that has good refractive index characteristics and high wet heat durability; and a curable composition. The present invention relates to: a compound represented by general formula (1); a curable composition which contains this compound; a semi-cured product; a cured product; an optical member; and a lens. In the formula, at least one of R1-R5 moieties represents a heteroaryl group or an aryl group that is substituted by a substituent containing a (meth)acryloyloxy group; and at least one of R6-R10 moieties represents an aryl group or a heteroaryl group. AA General formula (1)

Description

Curable composition, semi-cured product, cured product, optical member, lens and compound

The present invention relates to a curable composition, a semi-cured product obtained by curing the curable composition, and a cured product, an optical member and a lens including the cured product, and a compound used for the curable composition.

Conventionally, glass materials have been used for optical members of imaging modules such as cameras, video cameras, cellular phones with cameras, video phones, and door phones with cameras. Glass materials have various optical properties and have been preferably used because they are excellent in environmental resistance, but they have the disadvantage that they are not easy to reduce in weight and size and have poor processability and productivity. On the other hand, a resin cured product can be mass-produced and is excellent in processability, and has recently been used for various optical members.

In recent years, it has been required to miniaturize the optical member used for the imaging module with the miniaturization of the imaging module. However, as the optical member is miniaturized, the problem of chromatic aberration arises. For this reason, in the optical member using the resin cured product, the Abbe number (vd) and the partial dispersion ratio (θg, F) can be obtained by adding various additives to the curable composition to change the characteristics after curing. It is considered to make adjustments to correct the chromatic aberration.

Patent Document 1 describes a compound capable of providing an optical member having a high Abbe number (νd) and a high partial dispersion ratio (θg, F). This compound has a 4,4'-bis (aryl) diphenyl sulfone skeleton, and after containing the compound itself in a matrix polymer or polymerizing or copolymerizing the compound, it is suitable for the production of a complex lens, etc. The use is described.
On the other hand, for compounds having a skeleton similar to that of the 4,4'-bis (aryl) diphenyl sulfone skeleton, their refractive index characteristics and applications to optical members have hardly been studied. For example, Patent Document 2 discloses a compound having a 4,4'-bis (piperazino) dibenzophenone skeleton, but this document only describes the usefulness as a photopolymerization initiator, Nothing is mentioned about the usefulness as a compound for optical members.

JP, 2012-167019, A WO 2016/111923

When the present inventors re-tested the optical member described in Patent Document 1, it was found that there is a problem in wet heat durability when placed under high temperature and high humidity. Since the lens may be used under high temperature and high humidity depending on the element or device to be attached, the problem of the wet heat durability means that the application of the lens is greatly restricted. Moreover, also about the similar compound of patent document 2, it has a subject in wet heat durability from the structure, and it is estimated that a refractive index characteristic is also inferior.
In order to solve such problems of the prior art, the present inventors have developed an optical member having excellent refractive index characteristics and also excellent in wet heat durability, and providing such an optical member. We have made intensive studies to develop possible compounds and curable compositions.

As a result of intensive studies, the present inventors have found that use of a compound having a bis (aryl) benzophenone skeleton can provide an optical member having excellent wet heat durability and good refractive index characteristics. . As a result, the following invention has been provided as a specific means for solving the above problems.

[1] A curable composition containing a compound represented by the following general formula (1).

In the general formula (1),
R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent,
At least one of R ¹ to R ⁵ is an aryl group substituted with a (meth) acryloyloxy group-containing substituent or a heteroaryl group substituted with a (meth) acryloyloxy group-containing substituent,
At least one of R ⁶ to R ¹⁰ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ respectively They may be bonded to each other to form a linking group necessary to form a cyclic structure. However, the molecule represented by the general formula (1) does not include a polycyclic structure in which three or more aromatic rings are condensed.
[2] At least one of R ⁶ to R ¹⁰ is an aryl group substituted with a (meth) acryloyloxy group-containing substituent or a heteroaryl group substituted with a (meth) acryloyloxy group-containing substituent The curable composition as described in [1].
[3] The curable composition according to [1], wherein the compound is represented by the following general formula (2).

In the general formula (2),
R ^a and R ^b each independently represent a substituent other than an aryl group and a heteroaryl group,
n1 and n2 each independently represent an integer of 0 to 4. When n1 is 2 or more, plural ^Ras may be the same or different, and when n2 is 2 or more, The plurality of R ^b may be the same or different,
R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent,
At least one of R ¹¹ to R ¹⁵ is a substituent containing a (meth) acryloyloxy group.
R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , benzene ring Two R ^a each bonded to an adjacent ring skeleton-forming atom and two R ^b each bonded to an adjacent ring skeleton-forming atom of ^a benzene ring to each other to form a cyclic structure It may form a linking group. However, the molecule represented by the general formula (2) does not include a polycyclic structure in which three or more aromatic rings are condensed.
[4] The curable composition according to [1], wherein the compound is represented by the following general formula (3).

In the general formula (3),
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent other than an aryl group and a heteroaryl group,
R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent,
At least one of R ¹¹ to R ¹⁵ is a substituent containing a (meth) acryloyloxy group.
R ¹ and R ² , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ And R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may be bonded to each other to form a linking group necessary to form a cyclic structure. However, the molecule represented by the general formula (3) does not include a polycyclic structure in which three or more aromatic rings are condensed.
[5] The curable composition according to [3] or [4], wherein R ¹² is a substituent containing a (meth) acryloyloxy group.
[6] The curable composition according to any one of [3] to [5], wherein at least one of R ¹⁶ to R ²⁰ is a substituent containing a (meth) acryloyloxy group.
[7] The curable composition according to any one of [3] to [6], wherein R ¹¹ , R ¹⁵ , R ¹⁶ and R ²⁰ are hydrogen atoms.
[8] The curable composition according to any one of [1] to [7], wherein the substituent containing a (meth) acryloyloxy group is represented by the following general formula (4).

In the general formula (4),
Ac represents a (meth) acryloyloxy group,
L ¹ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent,
L ² represents a carbonyl group, an ether group, a thiocarbonyl group, a thioether group, or a linking group combining these groups,
L ³ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent,
m1 represents an integer of 0 to 10, and when m1 is 2 or more, a plurality of L ^{1 s} may be the same or different, and a plurality of L ^{2 s} may be the same or different May be
m2 represents 0 or 1;
* Represents a bonding site of a substituent containing a (meth) acryloyloxy group.
[9] The substituent containing a (meth) acryloyloxy group is (meth) acryloyloxyalkoxy group, (meth) acryloyloxyalkoxyalkyl group, (meth) acryloyloxyalkoxycarbonylalkyl group, (meth) acryloyloxyalkoxycarbonylacyloxy The curable composition as described in [8] which is a group or (meth) acryloyl oxy alkoxy carbonyl acyloxy alkyl group.
[10] The curable composition according to any one of [1] to [9], wherein the compound contains two or more substituents containing a (meth) acryloyloxy group in the molecule.
[11] The curable composition according to any one of [1] to [10], wherein the compound does not contain a polycyclic structure in which two or more aromatic rings are condensed in the molecule.
[12] The curable composition according to any one of [1] to [11], wherein the curable composition contains at least one selected from a photo radical polymerization initiator and a thermal radical polymerization initiator.
[13] A semi-cured product of the curable composition according to any one of [1] to [12].
[14] A cured product of the curable composition as described in any one of [1] to [12].
[15] An optical member comprising the cured product according to [14].
[16] A lens comprising the cured product according to [14].
[17] A compound represented by the above general formula (2).

By using a curable composition containing a compound represented by the general formula (1) or a compound represented by the general formula (1), an optical member having good refractive index characteristics and excellent wet heat durability is provided. be able to.

Hereinafter, the present invention will be described in detail. The description of the configuration requirements described below may be made based on typical embodiments and specific examples, but the present invention is not limited to such embodiments.

Explanation of Terms First, terms and symbols used in the present specification will be described.
In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
In the notation of groups in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. That is, unless it is described as "unsubstituted", it includes those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Moreover, when the carbon number of a group is described, the carbon number means the total carbon number including the carbon number of the substituent substituted to the group. For example, when the carbon number of an alkyl group is described, it means the total carbon number including the carbon number of the substituent substituted to the alkyl group.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, and “(meth) acryloyloxy” represents acryloyloxy and methacryloyloxy.
In the present specification, the “substituent” means a monovalent atom or monovalent atomic group other than a hydrogen atom. Preferred substituents include halogen atoms, hydroxyl groups, alkyl groups, alkenyl groups, alkoxy groups, alkylthio groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, aryl groups, heteroaryl groups, aryloxy groups, heteroaryloxy groups, and aryl groups. Examples thereof include an oxycarbonyl group, a heteroaryloxycarbonyl group, an arylthio group, a heteroarylthio group, a cyano group and an amino group. As a more preferable substituent, a hydroxyl group, an alkyl group, an alkoxy group and an alkylthio group can be mentioned.
In the present specification, the "halogen atom" is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
In the present specification, the "alkyl group" may be linear, branched or cyclic. In addition, two or more of the linear portion, the branched portion, and the cyclic portion may be mixed. Preferred are linear or branched alkyl groups. The carbon number of the alkyl group can be, for example, 1 or more, 2 or more, 4 or more, 6 or more. Moreover, carbon number can be 30 or less, 20 or less, and 10 or less. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, Examples thereof include 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group.
In the present specification, the "alkenyl group" may be linear, branched or cyclic. In addition, two or more of the linear portion, the branched portion, and the cyclic portion may be mixed. Preferred are linear or branched alkenyl groups. The carbon number of the alkenyl group can be, for example, 2 or more, 4 or more, 6 or more. Moreover, carbon number can be 30 or less, 20 or less, and 10 or less. Specific examples of the alkenyl group include ethenyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, t-butenyl group, n-pentenyl group, isopentenyl group, n-hexenyl group, isohexenyl group, Examples thereof include 2-ethylhexenyl group, cyclopentenyl group, cyclohexenyl group and cycloheptenyl group.
As used herein, "acyl group" is a generic term for alkylcarbonyl group, arylcarbonyl group and heteroarylcarbonyl group.
In the present specification, the "acyloxy group" is a generic term for an alkylcarbonyloxy group, an arylcarbonyloxy group and a heteroarylcarbonyloxy group.

In the present specification, the “aryl group” may be a group consisting of only one aromatic hydrocarbon ring or a group in which one or more rings are condensed to an aromatic hydrocarbon ring. When it is a group in which one or more rings are fused to an aromatic hydrocarbon ring, at least one of the aromatic hydrocarbon ring, the aliphatic hydrocarbon ring and the non-aromatic heterocycle is fused to the aromatic hydrocarbon ring Can be adopted. The carbon number of the aryl group can be, for example, 6 or more and 10 or more. Moreover, carbon number can be 30 or less, 18 or less, 14 or less, 10 or less. Specific examples of the aryl group include phenyl group, 1-naphthyl group and 2-naphthyl group.
In the present specification, the "heteroaryl group" may be a group consisting of only one heteroaromatic ring or a group in which one or more rings are condensed to a heteroaromatic ring. When it is a group in which one or more rings are fused to a heteroaromatic ring, at least one of an aromatic hydrocarbon ring, a heteroaromatic ring, an aliphatic hydrocarbon ring and a nonaromatic heterocycle is an aromatic hydrocarbon ring And the condensed group can be adopted. The ring skeleton forming atom number of the heteroaryl group can be, for example, 5 or more, 6 or more, 9 or more, 10 or more. In addition, the number of ring skeleton-forming atoms can be 30 or less, 18 or less, 14 or less, or 11 or less. The heteroaryl group may be a group bonded via a hetero atom or a group bonded via a carbon atom constituting a heteroaromatic ring. As a hetero atom which comprises the ring frame of the hetero aromatic ring of heteroaryl group, a nitrogen atom, an oxygen atom, and a sulfur atom can be mentioned, for example. Specific examples of the heteroaryl group include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4-pyrimidyl group, 5-pyrimidyl group and triazinyl group.
The "amino group" in the present specification includes a dialkylamino group and a diarylamino group. Two alkyl groups constituting a dialkylamino group may be bonded to each other to form a cyclic structure, and two aryl groups constituting a diarylamino group may be bonded to each other to form a cyclic structure.

Description and specific example of the alkyl part of "alkoxy group" in the present specification, description and specific example of the alkyl part of "alkylthio group" in the present specification, when "acyl group" in the present specification is an alkylcarbonyl group Description and specific examples of the alkyl moiety (a moiety obtained by removing a carbonyl group from an acyl group), an alkyl moiety (a moiety obtained by removing a carbonyloxy group from an acyl group) when the "acyloxy group" in the specification is an alkylcarbonyloxy group Description and specific examples, Description and specific examples of the alkyl part (the part which removed the oxycarbonyl group from the alkoxycarbonyl group) in the specification of this specification, the "amino group" in this specification is a dialkylamino group See the description and examples of alkyl groups above for each alkyl moiety at any given time. It can be.
Description and specific examples of the aryl moiety (a moiety obtained by removing a carbonyl group from an acyl group) when the "acyl group" in the present specification is an arylcarbonyl group, the "acyloxy group" in the present specification is an arylcarbonyloxy group Description and specific example of an aryl moiety (a moiety obtained by removing a carbonyloxy group from an acyl group), Description and specific examples of an aryl moiety of an "aryloxy group", an aryl moiety (aryloxycarbonyl group) of an "aryloxycarbonyl group" And the specific examples thereof, the description and specific examples of the aryl moiety of the “arylthio group” in the present specification, and the respective aryls when the “amino group” in the present specification is a diarylamino group For the part, reference can be made to the description and examples of the aryl group described above.
The description and specific examples of the heteroaryl moiety (the moiety obtained by removing a carbonyl group from an acyl group) when the "acyl group" in the present specification is a heteroarylcarbonyl group, the "acyloxy group" in the present specification is a heteroarylcarbonyloxy Description and specific examples of a heteroaryl moiety (a moiety obtained by removing a carbonyloxy group from an acyl group) when it is a group, Description and illustrative examples of a heteroaryl part of the "heteroaryloxy group" in the present specification, Description and specific examples of the heteroaryl part of the “heteroaryloxycarbonyl group” (the part in which the oxycarbonyl group has been removed from the heteroaryloxycarbonyl group), description and specific examples of the heteroaryl part of the “heteroarylthio group” in the present specification For examples, see the descriptions and examples of heteroaryl groups above. Rukoto can.
In the present specification, "n-" described before a chain substituent is an abbreviation for normal (straight chain), and "t-" is an abbreviation for tertiary.
In the present specification, “monomer” is a concept that is distinguished from oligomers and polymers, and refers to a monomer having a weight average molecular weight of 1,000 or less.

In the present specification, “refractive index (nd)”, “Abbe number (νd)” and “partial dispersion ratio (θg, F)” refer to a Calnew precision refractometer (Model No. KPR-2000, manufactured by Shimadzu Corporation). It is the value measured using. For the details of the measurement procedure, the descriptions in Examples 1 to 3 can be referred to. The “refractive index (nd)” in the present specification is a refractive index at a wavelength of 587.56 nm. Moreover, "Abbe number ((nu) d)" and "partial dispersion ratio ((theta) g, F)" are values calculated by the following formula from the refractive index measurement value in a different wavelength.
d d = (nd-1) / (nF-nC)
θg, F = (ng-nF) / (nF-nC)
Here, nd represents a refractive index at a wavelength of 587.56 nm, nF represents a refractive index at a wavelength of 486.13 nm, nC represents a refractive index at a wavelength of 656.27 nm, and ng represents a refractive index at a wavelength of 435.83 nm.

Compound (Definition) Represented by General Formula (1 )
The compound represented by the following general formula (1) will be described in detail.

In the general formula (1), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent. Provided that at least one of R ¹ to R ⁵ is an aryl group substituted with a (meth) acryloyloxy group-containing substituent or a heteroaryl group substituted with a (meth) acryloyloxy group-containing substituent is there. In addition, at least one of R ⁶ to R ¹⁰ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
Here, R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ Each may be bonded to each other to form a linking group necessary to form a cyclic structure. However, the molecule represented by the general formula (1) does not include a polycyclic structure in which three or more aromatic rings are condensed.

(Description of R ¹ to R ⁵ )
The “aryl group substituted with a substituent containing a (meth) acryloyloxy group” taken by at least one of R ¹ to R ⁵ or the “heteroaryl group substituted with a substituent containing a (meth) acryloyloxy group” is It is an aryl group or heteroaryl group having at least one substituent containing one or more (meth) acryloyloxy groups. Preferably, it is an aryl group or heteroaryl group having at least one substituent containing one (meth) acryloyloxy group, more preferably one or two substituents containing one (meth) acryloyloxy group Or an aryl or heteroaryl group having one or more substituents, more preferably an aryl or heteroaryl group having one substituent containing one (meth) acryloyloxy group. The aryl group or heteroaryl group may have a substituent other than the substituent including a (meth) acryloyloxy group. Preferred examples of such a substituent include a hydroxyl group, an alkyl group, an alkoxy group and an alkylthio group.
Preferably, one or two of R ¹ to R ⁵ are “aryl groups substituted with a substituent containing a (meth) acryloyloxy group” or “hetero substituted with a substituent containing a (meth) acryloyloxy group” It is a case where it is “aryl group”, more preferably, one or two of R ¹ to R ⁵ is “an aryl group substituted with a substituent including a (meth) acryloyloxy group”, more preferably This is the case where ^{one of} R ¹ to R ⁵ is “an aryl group substituted by a substituent containing a (meth) acryloyloxy group”.
Among R ¹ to R ⁵ , at least one of R ² to R ⁴ is substituted with “an aryl group substituted with a (meth) acryloyloxy group-containing substituent” or a “(meth) acryloyloxy group-containing substituent It is preferable that it is "heteroaryl group". In particular, at least one of R ² and R ⁴ is a “aryl group substituted with a (meth) acryloyloxy group-containing substituent” or a “heteroaryl group substituted with a (meth) acryloyloxy group-containing substituent” If it is, it is preferable because the solubility is further improved.
R ¹ to R ⁵ other than “aryl group substituted with a substituent containing a (meth) acryloyloxy group” or “heteroaryl group substituted with a substituent containing a (meth) acryloyloxy group” are other than these It is a substituent or a hydrogen atom. The number of substituents other than these is preferably 0 to 2 of R ¹ to R ⁵ and may be, for example, 0 or 1.

(Description of R ⁶ to R ¹⁰ )
The “aryl group” that can be taken by R ⁶ to R ¹⁰ may be an aryl group substituted with a substituent that includes a (meth) acryloyloxy group. In that case, it may be the same as or different from the “aryl group substituted with a substituent containing a (meth) acryloyloxy group” represented by any of R ¹ to R ⁵ . Preferred is when it is the same group.
Further, the "heteroaryl group" that can be taken by R ⁶ to R ¹⁰ may be a heteroaryl group substituted with a substituent including a (meth) acryloyloxy group. In that case, it may be the same group as “a heteroaryl group substituted by a substituent containing a (meth) acryloyloxy group” represented by any of R ¹ to R ⁵ , or may be a different group . Preferred is when it is the same group.
Among R ⁶ to R ¹⁰ , at least one of R ⁷ to R ⁹ is preferably an aryl group, for example, at least one of R ⁷ and R ⁹ is an aryl group, or R ⁸ is an aryl group The case can be mentioned. If at least one of R ⁷ and R ⁹ is an aryl group, the solubility tends to further increase, which is preferable.

(Substituent containing (meth) acryloyloxy group)
“(Meta) in“ aryl group substituted with a substituent containing a (meth) acryloyloxy group ”that can be taken by R ¹ to R ¹⁰ or“ heteroaryl group substituted with a substituent containing a (meth) acryloyloxy group ” The substituent containing an acryloyloxy group may be a group containing a (meth) acryloyloxy group, but is particularly preferably a group represented by the following general formula (4).

In the general formula (4),
Ac represents a (meth) acryloyloxy group,
L ¹ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent,
L ² represents a carbonyl group, an ether group, a thiocarbonyl group, a thioether group, or a linking group combining these groups,
L ³ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent,
m1 represents an integer of 0 to 10, and when m1 is 2 or more, a plurality of L ^{1 s} may be the same or different, and a plurality of L ^{2 s} may be the same or different May be
m2 represents 0 or 1;
* Represents a bonding site of a substituent containing a (meth) acryloyloxy group.

Formula number of carbon atoms of the alkylene ^{group L 1} can take the (4) is preferably from 2 to 6, 2 to 5 and more preferable. For example, ethylene group, 1-methylethylene group, 2-methylethylene group, n-propylene group, 2-methylpropylene group, 2,2-dimethylpropylene group and n-butylene group can be mentioned. Here, an alkylene group is described with the atom to be bonded to L ² as the 1-position. If L ¹ is a branched alkylene group, it is preferable in that the solubility is further improved.
m1 is preferably 1 to 5, more preferably 1 to 3, and may be 1 or 2. When m is 2 or more, a plurality of L ¹ may be the same or different, but are preferably the same. Moreover, although several L ² may also be the same or different, they are preferably the same.
The carbon number of the alkylene group that L ^{3 in the} general formula (4) can be is preferably 1 to 6, and more preferably 1 to 3. For example, methylene group, ethylene group, 1-methylethylene group, 2-methylethylene group, n-propylene group can be mentioned. Here, the alkylene group is described with the atom bonded to L ³ or the atom on the * mark side of General Formula (4) as the first position.
m2 may be either 0 or 1, but when it is 1, the alkylene groups represented by L ¹ and L ³ may be the same or different.
The following can be mentioned as specific examples of the linking group that L ² of General Formula (4) can be. The ** mark on the left side of each linking group indicates the bonding position to L ¹ , the ** mark on the right side indicates the bonding position to L ³ when m 2 is 1 and the general formula when m 2 is 0 It is synonymous with * of (4).
When m is 2 or more, a plurality of L ² may be the same or different.

Examples of “substituent containing (meth) acryloyloxy group” include (meth) acryloyloxyalkoxy group, (meth) acryloyloxyalkoxyalkyl group, (meth) acryloyloxyalkoxycarbonylalkyl group, (meth) acryloyloxyalkoxycarbonyl An acyloxy group or a (meth) acryloyloxy alkoxycarbonyl acyloxyalkyl group can be mentioned.
The chain length of the “substituent containing (meth) acryloyloxy group” is preferably 7 to 20, and more preferably 8 to 15. By increasing the chain length to the preferred range, the solubility of the compound can be improved.
The position at which the “substituent containing a (meth) acryloyloxy group” is bonded to the aryl group or the heteroaryl group may be any position of these aryl groups or heteroaryl groups, but any one of positions 3 to 5 Preferably it is one or more. In addition, here, the “aryl group substituted with a substituent containing a (meth) acryloyloxy group” or the “heteroaryl group substituted with a substituent containing a (meth) acryloyloxy group” is bonded to benzophenone 1 It is written as an atom of rank.
The number of “substituents containing (meth) acryloyloxy group” in the compound represented by the general formula (1) is preferably 2 or more, more preferably 2 to 4, and still more preferably 2 or 3.

Specific examples of the “substituent containing a (meth) acryloyloxy group” will be given below. However, the “substituent containing a (meth) acryloyloxy group” that can be adopted in the present invention is not limitedly interpreted by these specific examples. In the following structures, R represents a hydrogen atom or a methyl group, and the symbol * represents a bonding position to an aryl group or a heteroaryl group.

The following notation in the present application:

Indicates one of the following structures. That is, it shows a structure in which a methyl group is bonded to any one carbon atom constituting an oxyethyleneoxy group.

(Substituent which does not contain (meth) acryloyloxy group)
R ¹ to R ¹⁰ are not the above-mentioned “aryl group substituted by a substituent containing a (meth) acryloyloxy group” or “heteroaryl group substituted by a substituent containing a (meth) acryloyloxy group” It may be a group. As such substituent, a substituent which does not contain a (meth) acryloyloxy group can be mentioned. Moreover, a hydroxyl group, an alkyl group, an alkoxy group, and an alkylthio group can be mentioned as a preferable thing in such a substituent. From another viewpoint, as a preferable substituent, an alkyl group or a group represented by the following general formula (5) can be mentioned.

In the general formula (5),
T represents a hydrogen atom, a hydroxyl group or a halogen atom,
L ¹ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent,
L ² represents a carbonyl group, an ether group, a thiocarbonyl group, a thioether group, or a linking group combining these groups,
L ³ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent,
m1 represents an integer of 0 to 10, and when m1 is 2 or more, a plurality of L ^{1 s} may be the same or different, and a plurality of L ^{2 s} may be the same or different May be
m2 represents 0 or 1, and when T is a hydrogen atom and m1 is 0, m2 is 1;
* Indicates a bonding site of the substituent represented by the general formula (5).

For the description and specific examples of L ¹ , L ² , L ³ , m 1 and m ² in the general formula (5), the corresponding description in the general formula (4) can be referred to.
The following groups can be mentioned as specific examples of the group represented by the general formula (5). However, the groups that can be adopted in the present invention are not limitedly interpreted by the following specific examples.
HO- *
CH ₃ O- *
CH ₃ CH ₂ O- *
HOCH ₂ CH ₂ O- *
CH ₃ OCH ₂ CH ₂ O- *
CH ₃ S- *
CH ₃ CH ₂ S- *

(Formation of annular structure)
R ¹ and R ² in general formula (1), R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ And R ¹⁰ may be bonded to each other to form a linking group necessary to form a cyclic structure. The cyclic structure formed may be an aromatic ring or a non-aromatic ring. In addition, the cyclic structure to be formed may be a cyclic structure in which a ring skeleton forming atom is formed only of carbon atoms, or may be a cyclic structure including a hetero atom as a ring skeleton forming atom. Preferred is a cyclic structure in which the ring skeleton-forming atom is composed only of carbon atoms. As an example of the cyclic structure formed, a benzene ring, a pyridine ring, a pyrimidine ring and a cyclohexene ring can be mentioned. These rings may be substituted by a substituent. However, the molecule represented by the general formula (1) does not include a polycyclic structure in which three or more aromatic rings are condensed. In addition, it is preferable that any two of R ¹ to R ¹⁰ are not bonded to each other to form a cyclic structure.

(Conjugated system)
The compound represented by the general formula (1) has a conjugated system containing a benzophenone structure. The number of atoms constituting one conjugated system including the benzophenone structure (the number of conjugated system constituent atoms having π electron of the conjugated system) is preferably 24 to 38, more preferably 24 to 34, 34 is more preferable, and 26 to 32 is even more preferable. By appropriately controlling the number of atoms constituting one conjugated system including the benzophenone structure, it is possible to avoid the decrease in the solubility and the coloring of the compound. Among atoms constituting one conjugated system including a benzophenone structure, 1 to 7 hetero atoms are preferably contained, and 1 to 5 hetero atoms are more preferably contained, for example, 1 to 3 It is also possible to include.

(Symmetry)
The compounds represented by the general formula (1) are bonded to the left and right even if they are symmetrical compounds in which the groups bonded to the left and right of the carbonyl group described in the center of the general formula (1) are the same It may be an asymmetric compound in which the groups are different. Symmetrical compounds have the advantage of ease of synthesis.

Compound (Definition) Represented by General Formula (2 )
The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).

In the general formula (2),
R ^a and R ^b each independently represent a substituent other than an aryl group and a heteroaryl group,
n1 and n2 each independently represent an integer of 0 to 4. When n1 is 2 or more, plural ^Ras may be the same or different, and when n2 is 2 or more, The plurality of R ^b may be the same or different,
R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent,
At least one of R ¹¹ to R ¹⁵ is a substituent containing a (meth) acryloyloxy group.
R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , benzene ring Two R ^a each bonded to an adjacent ring skeleton-forming atom and two R ^b each bonded to an adjacent ring skeleton-forming atom of ^a benzene ring to each other to form a cyclic structure It may form a linking group. However, the molecule represented by the general formula (2) does not include a polycyclic structure in which three or more aromatic rings are condensed.

(Substituent of benzophenone)
The compound represented by the general formula (2) is a compound having a structure in which one substituted phenyl group is substituted on each benzene ring of benzophenone. The substitution position of the substituted phenyl group may be any position of the benzene ring of benzophenone. Each benzene ring of benzophenone may be substituted with R ^a and R ^b which are substituents other than the aryl group and the heteroaryl group. Substitution number n2 of substituents which n1 and ^{R b} in R ^a are each preferably independently 0-2, may be 0 or 1. The substitution position of the substituted phenyl group to each benzene ring of benzophenone is preferably either 3 to 5 or 3 'to 5', but the substitution position of R ^a and R ^b is 2 to 6 or 2 It may be any of the '6' positions.

(Description of R ^a and R ^b )
R ^a and R ^b are not particularly limited as long as they are substituents other than an aryl group and a heteroaryl group, but preferably a hydroxyl group, an alkyl group, an alkoxy group and an alkylthio group can be mentioned, more preferably And examples thereof include an alkyl group and an alkoxy group. As ^a specific example of the substituent which ^Ra and ^Rb can take, the group quoted as a specific example of the group represented with the said General formula (5) can be illustrated.

(Description of R ¹¹ to R ¹⁵ )
At least one of R ¹¹ to R ¹⁵ is a “substituent containing (meth) acryloyloxy group”. The “substituent containing (meth) acryloyloxy group” is preferably any one or more of R ¹² to R ¹⁴ . When R ¹² is used, it is preferable in that the solubility is good. The remaining R ¹¹ to R ¹⁵ other than the “substituent containing a (meth) acryloyloxy group” is a substituent other than the “substituent containing a (meth) acryloyloxy group” or a hydrogen atom. Of R ¹¹ to R ¹⁵ , the number of substituents other than “a substituent containing a (meth) acryloyloxy group” is preferably 0 to 2, and may be 0 or 1. As a specific substituent, a hydroxyl group, an alkyl group, an alkoxy group and an alkylthio group are preferable, and it is also preferable that these groups be substituted by an alkoxy group, an alkoxy alkylene oxy group, or a group having an alkylene oxy repeating unit. . Among R ¹¹ to R ¹⁵ , R ¹¹ and R ¹⁵ are preferably hydrogen atoms.

(Description of R ¹⁶ to R ²⁰ )
R ¹⁶ to R ²⁰ each independently represent a hydrogen atom or a substituent. At least one of R ¹⁶ to R ²⁰ is preferably a substituent, and the substituent may be “a substituent containing a (meth) acryloyloxy group”, and at least one is a “(meth) acryloyloxy group” It is preferable that it is "a substituent containing The “substituent containing a (meth) acryloyloxy group” represented by at least one of R ¹⁶ to R ²⁰ and the “substituent containing a (meth) acryloyloxy group” represented by at least one of R ¹¹ to R ¹⁵ are the same. Although they may be different, they are preferably the same. The number of substituents other than “a substituent containing a (meth) acryloyloxy group” that can be taken by R ¹⁶ to R ²⁰ is preferably 0 to 2, and may be, for example, 0 or 1. The carbon number of substituents other than “a substituent containing a (meth) acryloyloxy group” is preferably 1 to 10. As a specific substituent, a hydroxyl group, an alkyl group, an alkoxy group and an alkylthio group are preferable, and it is also preferable that these groups be substituted by an alkoxy group, an alkoxy alkylene oxy group, or a group having an alkylene oxy repeating unit. . Among R ¹⁶ to R ²⁰ , R ¹⁶ and R ²⁰ are preferably hydrogen atoms.

Descriptions and specific examples of “substituents containing (meth) acryloyloxy group” that can be taken by R ¹¹ to R ²⁰ , and descriptions and specific examples of cyclic structures that can be formed by combining R ¹¹ and R ¹² with each other, The corresponding description in the description of the general formula (1) can be referred to.

Compound (Definition) Represented by General Formula (3 )
The compounds represented by the general formula (1) include compounds represented by the following general formula (3).

In the general formula (3),
R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent other than an aryl group and a heteroaryl group,
R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent,
At least one of R ¹¹ to R ¹⁵ is a substituent containing a (meth) acryloyloxy group.
R ¹ and R ² , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ And R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may be bonded to each other to form a linking group necessary to form a cyclic structure. However, the molecule represented by the general formula (3) does not include a polycyclic structure in which three or more aromatic rings are condensed.

(Description)
The compound represented by the general formula (3) is a compound having a structure in which a substituted phenyl group is substituted at the 4-position and 4'-position of benzophenone. Descriptions and specific examples of R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ^{10 in} the general formula (3) are the descriptions of R ^a and R ^{b in} the general formula (2) And specific examples can be referred to. For the description and specific examples of R ¹¹ to R ^{20 in} the general formula (3), the corresponding description of the general formula (2) can be referred to. Further, for the description and specific examples of the cyclic structure which may be formed by bonding R ¹ and R ² to each other, the corresponding description of the general formula (1) can be referred to.

Specific Examples Specific examples of the compound represented by the general formula (1) are given below. However, the compound represented by General formula (1) which can be employ | adopted by this invention is not limitedly interpreted by these examples. Me represents a methyl group.

Synthetic Methods The compounds represented by the general formula (1) can be synthesized by appropriately combining known synthetic methods.
For example, a compound in which a halogen atom is substituted with a hydroxyphenyl group can be synthesized first by selecting benzophenone having a halogen atom-substituted position as a position to introduce a substituent as a starting material and reacting with benzophenone. . Next, the hydroxyl group of the synthesized compound is reacted with a hydroxyalkyl halide to convert the hydroxyl group to a hydroxyalkoxy group, and further reacted with an acryloyl halide to give an acryloyl group at the terminal, which is represented by the general formula (1) Compounds can be synthesized. Each of these steps is a well-known synthesis reaction, and the reaction conditions and the like can be appropriately adjusted and optimized within a generally known range.
For specific synthetic procedures of the compound represented by the general formula (1), the following Examples 1 to 3 can be referred to.

Properties of Compound The compound represented by the general formula (1) exhibits excellent refractive index properties without curing. That is, the compound represented by the general formula (1) exhibits a high refractive index (nd), a low Abbe number (νd), a high partial dispersion ratio (θg, F), and a compound for an optical member without curing the compound. It is also possible to use as.
Although the Abbe number (dd) of the compound represented by the general formula (1) is not particularly limited, the Abbe number of the film formed by dissolving the compound in an appropriate solvent such as propylene glycol monomethyl ether acetate is It is preferably 25 or less, more preferably 20 or less, still more preferably 19 or less, and particularly preferably 18 or less. By keeping the Abbe number (vd) low, it is possible to correct chromatic aberration over a wide wavelength range.
Also, the partial dispersion ratio (θg, F) of the compound represented by the general formula (1) is not particularly limited, but the Abbe number of the film formed by dissolving the compound in an appropriate solvent is the partial dispersion The ratio (θg, F) is preferably 0.70 or more, more preferably 0.73 or more, and still more preferably 0.77 or more. By increasing the partial dispersion ratio (θg, F), it is possible to effectively correct the chromatic aberration particularly at a short wavelength.

When using as a compound for optical members, without hardening the compound represented by General formula (1), a compound can be disperse | distributed to matrix polymer and it can be used. As the matrix polymer, the materials described in paragraph 0098 of JP 2012-167019 A, which is incorporated herein by reference as part of the present specification, can be used. These materials may be used alone or in combination of two or more. When selecting a matrix polymer, it is preferable to select in consideration of the compatibility with the compound represented by the general formula (1). When the compound is dispersed in the matrix polymer, the content of the compound is preferably 1 to 70% by mass, and more preferably 5 to 50% by mass.

By curing the compound represented by the curable composition general formula (1), it is possible to form a cured product excellent in refractive index characteristics and also excellent in wet heat stability. In the case of curing, it is preferable to prepare a curable composition containing the compound represented by the general formula (1) and cure it.
The content of the compound represented by the general formula (1) in the curable composition is preferably 1 to 99% by mass, and preferably 10 to 90% by mass, based on the total mass of the curable composition. More preferably, it is 20 to 80% by mass.
The curable composition can contain various components in addition to the compound represented by the general formula (1). For example, (meth) acrylate monomers other than the compound represented by General formula (1), a polymerization control agent, and a polymerization initiator can be preferably contained. As the polymerization initiator, it is preferable to use at least one selected from a photo radical polymerization initiator and a thermal radical polymerization initiator. The curable composition can also contain a polymer having a radically polymerizable group in the side chain. These components are described in detail below.

((Meth) acrylate monomer)
The (meth) acrylate monomer that can be used in the curable composition of the present invention may be a polyfunctional (meth) acrylate monomer having two or more (meth) acryloyl groups in the molecule, and It may be a monofunctional (meth) acrylate monomer having two (meth) acryloyl groups.
Specific examples of the (meth) acrylate monomer include the (meth) acrylate monomers described in paragraphs 0037 to 0046 of JP 2012-107191 A, which are incorporated herein by reference as a part of this specification.

Examples of (meth) acrylate monomers that can be preferably used in the present invention include monofunctional (meth) acrylate monomers having an aromatic ring represented by monomer 1 (phenoxyethyl acrylate) or monomer 2 (benzyl acrylate), and monomer 3 Bifunctional (meth) acrylate monomer having an aliphatic ring represented by (tricyclodecane dimethanol diacrylate), monofunctional (meth) acrylate monomer having an aliphatic ring represented by monomer 4 (dicyclopentanyl acrylate) Can be mentioned. The molecular weight of the (meth) acrylate monomer is preferably 100 to 500.

There is no restriction | limiting in particular about the acquisition method of a (meth) acrylate monomer, You may obtain commercially and may manufacture synthetically. When obtained commercially, for example, Biscoat # 192 PEA (Monomer 1) (Osaka Organic Chemical Industry Ltd.), Biscoat # 160 BZA (Monomer 2) (Osaka Organic Chemical Industry Ltd.), A-DCP Monomer 3) (manufactured by Shin-Nakamura Chemical Co., Ltd.) and FA-513AS (monomer 4) (manufactured by Hitachi Chemical Co., Ltd.) can be preferably used.

When the curable composition of the present invention contains a (meth) acrylate monomer, the content of the (meth) acrylate monomer is preferably 1 to 80% by mass with respect to the total mass of the curable composition, It is more preferably 2 to 50% by mass, and still more preferably 3 to 40% by mass.

(Polymerization control agent)
In the curable composition of the present invention, a compound having a function of controlling the polymerization of the polymerizable component of the curable composition can be used as a polymerization control agent. As a preferable polymerization control agent, for example, a non-conjugated vinylidene group-containing compound can be adopted. As the non-conjugated vinylidene group-containing compound, the compounds described in paragraphs 0016 to 0033 of JP 2012-107191 A, which are incorporated herein by reference as a part of this specification, can be used. The molecular weight of the non-conjugated vinylidene group-containing compound is preferably 100 to 400, more preferably 120 to 350, and particularly preferably 130 to 300. There is no restriction | limiting in particular about the acquisition method of a nonconjugated vinylidene group containing compound, You may obtain commercially and may manufacture synthetically. When obtained commercially, for example, β-caryophyllene (manufactured by Inoue Perfume Manufacturing Co., Ltd.) or (+)-Limonen (manufactured by Tokyo Chemical Industry Co., Ltd.) can be preferably used.
When the curable composition of the present invention contains a non-conjugated vinylidene group-containing compound, the content of the non-conjugated vinylidene group-containing compound is 0.5 to 30% by mass based on the total mass of the curable composition. Is preferable, 1 to 25% by mass is more preferable, and 2 to 20% by mass is more preferable.

(Thermal radical polymerization initiator)
As a thermal radical polymerization initiator which can be used for the curable composition of the present invention, for example, 1,1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2, 2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butyl peroxy laurate , Dicumyl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, cumene hydroperoxide, t-butyl hydroperoxide, t-Butylperoxy-2-ethylhexyl, 2,3-di Mention may be made of a chill-2,3-diphenyl butane and the like.

Among them, the curable composition of the present invention preferably contains a hydroperoxide compound as a thermal radical polymerization initiator. The hydroperoxide compound is a peroxide and is a compound having a peroxy group. In the hydroperoxide compound, one oxygen atom of a peroxy group (—O—O—) is substituted with a hydrogen atom, and includes a hydroperoxide group (—O—O—H). The hydroperoxide compound having a hydroperoxide group in the molecule has the effect of promoting chain transfer during polymerization of the non-conjugated vinylidene group-containing compound, and the controllability of the three-dimensional structure when the curable composition cures is more It is possible to improve and impart deformability to the semi-cured product.

There is no restriction | limiting in particular about the acquisition method of a hydroperoxide compound, You may obtain commercially and may manufacture synthetically. When commercially obtained, for example, Park Mill H-80 (cumene hydroperoxide) manufactured by NOF Corporation can be used.

As a thermal radical polymerization initiator, it is preferable to contain a hydroperoxide compound and other thermal radical polymerization initiators. As other thermal radical polymerization initiators, non-hydroperoxide compounds can be mentioned. The hydroperoxide compound generally contains a non-hydroperoxide compound having a low thermal polymerization initiation temperature, since the temperature for initiating the thermal radical polymerization is generally high. As the non-hydroperoxide compound, t-butylperoxy-2-ethylhexanoate (manufactured by Nippon Oil and Fats Co., Ltd., Perbutyl O), t-butylperoxy-2-ethylhexyl carbonate (manufactured by Nippon Oil and Fats Co., Ltd., Perbutyl E) It is preferable to use a peroxyester compound such as

The content of the thermal radical polymerization initiator is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5.0% by mass, based on the total mass of the curable composition. More preferably, it is 0.05 to 2.0% by mass.
By thermally polymerizing a curable composition containing a thermal radical polymerization initiator, a cured product having high heat resistance can be formed.

(Photo radical polymerization initiator)
As a radical photopolymerization initiator which can be used for the curable composition of the present invention, for example, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethylbenzoyl) ) -2,4,4-trimethylpentyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) -2,4,4-trimethylpentyl phosphine oxide, bis (2,6-dichloro benzoyl) -2,4 , 4-trimethylpentyl phosphine oxide, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1,2-diphenylethanedione, methylphenylglyoxyl , 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-) 2-Methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl) ) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis Examples include (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide and the like.

Among them, in the present invention, IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone), IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), IRGACURE 651, manufactured by BASF AG, as a photo radical polymerization initiator. (2,2-dimethoxy-1,2-diphenylethane-1-one), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one can be preferably used.

The content of the photoradical polymerization initiator is preferably 0.01 to 5.0% by mass, and more preferably 0.05 to 1.0% by mass, based on the total mass of the curable composition. Preferably, it is more preferably 0.05 to 0.5% by mass.
In addition, it is preferable that a curable composition contains both an optical radical polymerization initiator and a thermal radical polymerization initiator, and in this case, the total content of an optical radical polymerization initiator and a thermal radical polymerization initiator is a curable composition. 0.01 to 10% by mass, preferably 0.05 to 5.0% by mass, and more preferably 0.05 to 3.0% by mass with respect to the total mass of More preferable.

(Polymer having a radically polymerizable group in the side chain)
The polymer having a radically polymerizable group in the side chain functions to increase the viscosity of the curable composition, and thus functions as a thickener or a thickening polymer. Therefore, it is possible to adjust the viscosity of the curable composition within a desired range by adding an appropriate amount of a polymer having a radically polymerizable group in the side chain to the curable composition.

The polymer having a radically polymerizable group in the side chain may be a homopolymer or a copolymer. Among them, the polymer having a radically polymerizable group in the side chain is preferably a copolymer. When the polymer having a radically polymerizable group in the side chain is a copolymer, at least one of the copolymer components may have a radically polymerizable group. Moreover, when the polymer which has a radically polymerizable group in a side chain is a copolymer, it contains the monomer unit which has a radically polymerizable group in a side chain, and the monomer unit which has an aryl group in a side chain. It is more preferable that it is a copolymer.

As a radically polymerizable group, a (meth) acrylate group, a vinyl group, a styryl group, an allyl group etc. can be mentioned. The polymer having a radically polymerizable group in the side chain preferably contains 5 to 100% by mass, and more preferably 10 to 90% by mass of repeating units having a radically polymerizable group. And 20 to 80% by mass is more preferable.

In the following, specific examples of the polymer having a radically polymerizable group in a side chain preferably used in the present invention will be listed, but the polymer having a radically polymerizable group in a side chain is not limited to the following structure .
In the following structural formulas, Ra and Rb each independently represent hydrogen or a methyl group. In addition, several Ra in one polymer may be the same or different. In addition, n represents an integer of 0 to 10, preferably 0 to 2, and more preferably 0 or 1.

 

The molecular weight (weight average molecular weight) of the polymer having a radically polymerizable group in the side chain is preferably 1,000 to 10,000,000, and more preferably 5,000 to 300,000. More preferably, it is 2,000 to 200,000. The glass transition temperature of the polymer having a radically polymerizable group in the side chain is preferably 50 to 400 ° C., more preferably 70 to 350 ° C., and still more preferably 100 to 300 ° C. .

The content of the polymer having a radically polymerizable group in the side chain is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the curable composition. It is further preferable that the content is less than or equal to%. In addition, 0 mass% may be sufficient as content of the polymer which has a radically polymerizable group in a side chain, and the aspect which does not add the polymer which has a radically polymerizable group in a side chain is also preferable.

(Other additives)
The curable composition may contain additives such as polymers, monomers, dispersants, plasticizers, heat stabilizers, and mold release agents other than the components described above unless it is not against the spirit of the present invention.

(viscosity)
The viscosity of the curable composition of the present invention is preferably 20,000 mPa · s or less, more preferably 15,000 mPa · s or less, and still more preferably 13,000 mPa · s or less. It is particularly preferable that the viscosity is not more than 1,000 mPa · s. By setting the viscosity of the curable composition within the above range, the handleability at the time of molding the cured product can be enhanced, and a high quality cured product can be formed. The viscosity of the curable composition is preferably 2,000 mPa · s or more, more preferably 3,000 mPa · s or more, and still more preferably 4,000 mPa · s or more, 5, It is particularly preferable that the viscosity is at least 000 mPa · s.

Method for Producing Cured Product A cured product can be produced by curing the curable composition of the present invention. At the time of producing a cured product, at least one of the step of photocuring and the step of thermally curing is performed. In addition, when producing a cured product, a step of forming a semi-cured product by irradiating the curable composition with light or heating the curable composition and irradiating the resulting semi-cured product with light Alternatively, it is preferable to sequentially perform the steps of forming a cured product by heating the semi-cured product.

(Step of forming a semi-cured product)
Preferably, the step of forming the semi-cured product first includes a transfer step. The transfer step is a step of pressing a mold against the curable composition described above. In the transfer step, the other mold is pressed against the curable composition injected into one of the pair of molds to push and spread the curable composition.

It is preferable that the metal mold | die used by the manufacturing method of hardened | cured material is what the chromium nitride process was given. As a result, good mold releasability can be obtained in the subsequent mold release step, and the manufacturing efficiency of the optical member can be enhanced.

Examples of the chromium nitride treatment include a method of forming a chromium nitride film on the surface of a mold. As a method of forming a chromium nitride film on the surface of a mold, for example, there are a CVD (Chemical Vapor Deposition) method and a PVD (Physical Vapor Deposition) method. The CVD method is a method of forming a chromium nitride film on the surface of a substrate by reacting a source gas containing chromium and a source gas containing nitrogen at a high temperature. The PVD method is a method (arc vacuum deposition method) of forming a chromium nitride film on a substrate surface using arc discharge. In this arc-type vacuum evaporation method, a cathode (evaporation source) made of, for example, chromium is disposed in a vacuum vessel, and arc discharge is caused between the cathode and the wall of the vacuum vessel through a trigger to evaporate the cathode. At the same time, metal ionization is performed by arc plasma, a negative voltage is applied to the substrate, and the reaction gas, for example, nitrogen gas, is put into a vacuum vessel at several tens mTorr (1.33 Pa) to ionize the metal and the reaction gas. It is a method of making it react on the surface of to make a film of a compound. The chromium nitride treatment of the mold surface in the present specification is carried out by the above-mentioned CVD method or PVD method.

Here, the mold is generally combined with two molds and can be heated while pressurizing the contents, and when a composition of low viscosity is injected into the mold, the mold clearance is obtained. Cause a leak. For this reason, the curable composition injected into the mold preferably has a viscosity of a certain level or more. In order to adjust the viscosity of the curable composition, a polymer having the above-described radical polymerizable group in the side chain may be added to the curable composition.

After the step of pressing the mold, a step of forming a semi-cured product is performed. The semi-cured product is obtained by semi-curing the curable composition injected into the mold. In the step of forming the semi-cured product, light irradiation or heating is performed. In the present specification, such a process can also be referred to as a semi-curing process.

In the step of forming the semi-cured product, at least one of light irradiation and heating is performed on the curable composition of the present invention to obtain a half of complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and 10 Hz frequency. It is preferable to form a cured product.

Here, in the present specification, the term "semi-cured product" refers to a product obtained by polymerizing the curable composition, not completely solid, and having a certain degree of fluidity. When the complex viscosity of the polymer of the curable composition at 10 ° C. and a frequency of 10 Hz is 10 ⁵ to 10 ⁸ mPa · s, the polymer is a semi-cured product. That is, up to less than 1.0 × 10 ⁹ mPa · s can be regarded as a semi-cured product as the upper limit value of the complex viscosity at 25 ° C. and a frequency of 10 Hz. On the other hand, the "cured product" is a product obtained by curing the curable composition by polymerization and means a product in a completely solid state.

The light used for light irradiation is preferably ultraviolet light or visible light, and more preferably ultraviolet light. For example, metal halide lamps, low pressure mercury lamps, high pressure mercury lamps, super high pressure mercury lamps, germicidal lamps, xenon lamps, LED (light emitting diode) light source lamps and the like are suitably used. The atmosphere at the time of light irradiation is preferably air or an inert gas replacement atmosphere, and more preferably an atmosphere purged with nitrogen until the oxygen concentration is 1% or less.

In the semi-curing step, when the heating and semi-curing step is provided, the heating and semi-curing should be carried out so that the complex viscosity at 25 ° C. and frequency 10 Hz of the semi-cured product after heating is 10 ⁵ to 10 ⁸ mPa · s. preferable.

The present invention may relate to a semi-cured product produced by the method described above. Such a semi-cured product can be preferably used in the method for producing a cured product described later. Here, the preferred range of the complex viscosity of the semi-cured product is the same as the preferred range of the complex viscosity of the semi-cured product in the step of forming the semi-cured product described above.

In the semi-cured product, after the light irradiation step, all of the photo radical polymerization initiator may be consumed and may not be contained at all, and the photo radical polymerization initiator may remain.

The glass transition temperature of the semi-cured product is preferably −150 to 0 ° C., more preferably −50 to 0 ° C., and particularly preferably −20 to 0 ° C.

(Step of forming a cured product)
The step of forming the cured product includes a polymerization step of obtaining the cured product by putting the semi-cured product in a mold and deforming under pressure, heating and thermally polymerizing, or photopolymerization by light irradiation. Is preferred. Such a process can also be referred to herein as a curing process. The conditions for light irradiation and the heating conditions in the step of forming a cured product are the same as the conditions in the above-described semi-curing step.

When the curing step is a thermal polymerization step, the mold used in the polymerization step is also referred to as a thermoforming mold. In general, a thermoforming mold is preferably configured to be capable of heating while pressing the contents while combining two molds. In the method of producing a cured product, it is more preferable to use a mold as a mold in the thermal polymerization step for obtaining the cured product. As such a thermoforming molding die, for example, the one described in JP-A-2009-126011 can be used. Moreover, it is preferable that a metal mold | die is what chromium nitride process was given.

In the thermal polymerization step, the semi-cured product placed in the mold is pressure-deformed and heated to thermally polymerize to obtain a cured product. Here, pressure deformation and heating may be performed simultaneously, heating may be performed after pressure deformation, and pressure deformation may be performed after heating. Among them, pressure deformation and heating may be performed. It is preferable to carry out simultaneously. Moreover, it is also preferable to perform heating at a higher temperature after the pressurization is stabilized after simultaneously performing the pressure deformation and the heating.

In the thermal polymerization step, the semi-cured product is cured by heating at a temperature of 150 ° C. or higher to obtain a cured product.
The heating temperature is 150 ° C. or higher, preferably 160 to 270 ° C., more preferably 165 to 250 ° C., and still more preferably 170 to 230 ° C.
In this curing step, it is preferable to perform heating and pressure deformation. This makes it possible to accurately transfer the inverted shape of the inner surface of the mold to the cured product.

The pressure in the pressure deformation is preferably 0.098 MPa to 9.8 MPa, more preferably 0.294 MPa to 4.9 MPa, and particularly preferably 0.294 MPa to 2.94 MPa.
The thermal polymerization time is preferably 30 to 1000 seconds, more preferably 30 to 500 seconds, and particularly preferably 60 to 300 seconds. The atmosphere at the time of thermal polymerization is preferably air or an inert gas-substituted atmosphere, and more preferably an atmosphere purged with nitrogen to an oxygen concentration of 1% or less.

After the curing step, a release step is provided. When thermal polymerization is performed in the curing step, it is preferable to separate the mold from the cured product in a temperature range of 150 to 250 ° C. in the release step. By setting the temperature in the release step within the above range, the mold can be easily separated from the cured product, and the production efficiency can be enhanced.

As mentioned above, although an example of the manufacturing method of hardened material of the present invention was explained, the composition of the present invention is not limited to this, and can be changed suitably in the range which does not deviate from the present invention. For example, the mold used in the transfer step and the semi-curing step may be used as it is in the curing step, and after performing the semi-curing step, the mold is pulled away from the semi-cured product It may be moved to a (thermoforming mold) to carry out a curing step. In this case, it is preferable that the above-described chromium treatment is applied to the mold used in the semi-curing step and the curing step.
In the semi-curing step, the curable composition in the mold may be irradiated with light and heated. This makes it possible to reliably obtain a semi-cured product having a desired degree of curing. The semi-cured product preferably has a complex viscosity of 10 ⁵ to 10 ⁸ mPa · s at 25 ° C. and a frequency of 10 Hz.

Cured Product The cured product of the present invention obtained by curing the curable composition containing the compound represented by the general formula (1) has excellent refractive index characteristics and wet heat durability. That is, the cured product of the present invention has a high refractive index (nd), a low Abbe number (vd), and a high partial dispersion ratio (θg, F).

The Abbe number (νd) of the cured product of the present invention is not particularly limited, but is preferably 30 or less, more preferably 27 or less, still more preferably 25 or less, and 23 or less. Being particularly preferred. By keeping the Abbe number (vd) low, it is possible to correct chromatic aberration over a wide wavelength range.
The partial dispersion ratio (θg, F) of the cured product of the present invention is also not particularly limited, but is preferably 0.68 or more, more preferably 0.70 or more, and 0.72 It is more preferable that it is more than. By increasing the partial dispersion ratio (θg, F), it is possible to effectively correct the chromatic aberration particularly at a short wavelength.

The cured product of the present invention is also excellent in wet heat durability. Therefore, it can be effectively used for a lens etc. which may be used under high temperature and high humidity.

The cured product of the present invention preferably has a maximum thickness of 0.1 to 10 mm. The maximum thickness is more preferably 0.1 to 5 mm, particularly preferably 0.15 to 3 mm. The cured product of the present invention preferably has a maximum diameter of 1 to 1000 mm. The maximum diameter is more preferably 2 to 200 mm, particularly preferably 2.5 to 100 mm.

Optical Member The present invention also relates to an optical member containing the above-mentioned cured product. The cured product of the present invention is a molded product having excellent optical properties, and thus is preferably used for an optical member. The type of the optical member of the present invention is not particularly limited. In particular, it can be suitably used as an optical member utilizing the excellent optical properties of the curable composition, in particular, an optical member transmitting light (so-called passive optical member). As an optical functional device provided with such an optical member, for example, various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP (Overhead projector), liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, An optical amplifier etc.), a camera, an imaging device such as a video, etc. are exemplified.

Moreover, as a passive optical member used for an optical function apparatus, a lens, a prism, a prism sheet, a panel (plate-shaped molded object), a film, an optical waveguide (film shape, fiber shape etc.), an optical disk, sealing of LED is mentioned, for example. An agent etc. are illustrated. Such a passive optical member may be provided with an optional coating layer, for example, a protective layer for preventing mechanical damage to the coated surface due to friction or abrasion, an undesirable wavelength of an inorganic particle, a base material, etc. A light absorption layer that absorbs light, a transmission shielding layer that suppresses or prevents transmission of reactive low molecules such as moisture and oxygen gas, an antiglare layer, an antireflective layer, a low refractive index layer, etc. It may be provided. Specific examples of the optional covering layer include a transparent conductive film or a gas barrier film formed of an inorganic oxide coating layer, a gas barrier film or a hard coat film formed of an organic coating layer, and the like. As a coating method for forming a coating layer, well-known coating methods, such as a vacuum evaporation method, CVD method, sputtering method, a dip coating method, a spin coat method, can be used.

The optical member using the cured product of the present invention is particularly preferably used for a lens substrate. A lens substrate produced using the curable composition of the present invention has a low Abbe number, and preferably has high refractive index, light transmittance, and light weight, and is excellent in optical properties. Moreover, it is possible to adjust the refractive index of a lens base material arbitrarily by adjusting the kind of monomer which comprises a curable composition suitably.
In the present specification, "lens substrate" means a single member capable of exhibiting a lens function. A film or a member can be provided on the surface or the periphery of the lens base according to the use environment or application of the lens. For example, a protective film, an antireflective film, a hard coat film or the like can be formed on the surface of the lens substrate. Moreover, it can be set as the composite lens laminated | stacked on the glass lens base material and the plastic lens base material. Furthermore, the periphery of the lens substrate can be inserted into and fixed to a substrate holding frame or the like. However, these films, frames, and the like are members added to the lens base material, and are distinguished from the lens base material itself referred to in the present specification.

When the lens substrate is used as a lens, the lens substrate itself may be used alone as a lens, or the above-described film or frame, or any other lens substrate may be added and used as a lens. The type and shape of the lens using the lens substrate are not particularly limited.
The lens substrate is preferably used for an imaging lens such as a mobile phone or a digital camera, a television, an imaging lens such as a video camera, and an in-vehicle lens or an endoscope lens.

The features of the present invention will be more specifically described below with reference to examples and comparative examples. The kind of material, the amount of use of the material, the treatment contents, the treatment procedure and the like described in the examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.

Synthesis of Compound (Example 1) Synthesis of Compound A-2

(1-1) Synthesis of Intermediate 1 In a 1 L three-necked flask, 6.8 g of 4,4'-dibromobenzophenone, 8.3 g of p-hydroxyphenylboronic acid, and 200 mL of 1,4-dioxane in a nitrogen stream, 100 mL of saturated sodium hydrogencarbonate aqueous solution was added, and it stirred at room temperature for 30 minutes. Thereafter, 0.6 g of bis (di-t-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) [(AMPHOS) ₂ PdCl ₂ ] was added, and the reaction was carried out at 90 ° C. for 3 hours. After confirming the progress of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature. The precipitated solid was collected by filtration and dissolved in tetrahydrofuran. The resultant was filtered through silica gel, hexane was added to the filtrate, and recrystallization was performed to obtain 6.7 g of Intermediate 1.

(1-2) Synthesis of Intermediate 2 In a 200 mL three-necked flask, 40 mL of dimethylformamide (DMF) and 0.48 g (oil, 60%) of sodium hydride (NaH) were added and stirred in an ice bath for 10 minutes did. After 2.0 g of Intermediate 1 was added thereto and stirred at room temperature for 1 hour, 1.7 g of 3-bromo-1-propanol was added. The temperature was raised to 50 ° C., and after 4 hours, a small amount of water was added to stop the reaction. The reaction mixture was diluted with ethyl acetate, washed with water and saturated brine, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, hexane was added to the filtrate, and recrystallization was performed to obtain 1.0 g of Intermediate 2.

(1-3) Synthesis of Compound A-2 In a 100 mL three-necked flask, 1.0 g of Intermediate 2, 10 mg of p-methoxyphenol (MEHQ), 10 mL of tetrahydrofuran (THF) and 1.6 mL of triethylamine (TEA) in a three-necked flask In addition, it was stirred for 10 minutes in an ice bath. To this was added 1.0 g of methacrylic acid chloride, and allowed to react at room temperature for 4 hours, and then a small amount of water was added to stop the reaction. The reaction mixture was diluted with ethyl acetate, washed with water and saturated brine, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, hexane was added to the filtrate, and recrystallization was performed to obtain 0.6 g of a compound A-2. The ¹ H-NMR (Nuclear Magnetic Resonance) data of Compound A-2 are as follows.
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 1.88 (s, 6 H), 2.05-2.15 ppm (m, 4 H), 4.20-4.35 ppm (m, 4 H), 4. 50-4.65 ppm (m, 4 H), 5.70 ppm (s, 2 H), 6.05 ppm (s, 2 H), 7.00-7.15 ppm (d, 2 H), 7.25-7.35 ppm d, 2H), 7.60-7.80 ppm (m, 8 H), 7.85-8.00 ppm (m, 4 H)

Example 2 Synthesis of Compound A-4

(2-1) Synthesis of Compound B In a 2 L three-necked flask, 100 g of 2-hydroxyethyl acrylate was added, and 132 mL of triethylamine and 650 mL of butyl acetate were added and stirred. While maintaining the reaction solution at 5 ° C., 70 mL of methanesulfonic acid chloride was added dropwise over 1 hour. After stirring for 1 hour, 500 mL of water was added to the reaction solution, and after stirring, the operation of removing the aqueous layer was repeated three times. Next, 30 mg of dibutyl hydroxytoluene was added, and then butyl acetate was distilled off under reduced pressure to obtain 160 g of compound B.

(2-2) Synthesis of Compound A-4 In a 500 mL three-necked flask, 5.0 g of Intermediate 1, 50 mL of tetrahydrofuran (THF), 0.05 mL of nitrobenzene, 13.3 g of cesium carbonate (Cs ₂ CO ₃ ) And 0.4 g of tetrabutylammonium bromide (TBAB) were added and stirred. To this was added 9.0 g of compound B, and the reaction was carried out for 5 hours while maintaining at 80 ° C. After cooling the reaction solution to room temperature, 300 mL of water was added, and the precipitated crude crystals were collected by filtration. The crude crystals were dissolved in tetrahydrofuran, methanol was added and recrystallized to obtain 6.5 g of compound A-4. The ¹ H-NMR (Nuclear Magnetic Resonance) data of Compound A-4 were as follows.
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 4.22-4.38 ppm (m, 4 H), 4.55-4. 70 ppm (m, 4 H), 5.85-5. 95 ppm (d, 2 H) ), 6.15-6.30 ppm (m, 2 H), 6.45-6. 55 ppm (d, 2 H), 7.00-7. 15 ppm (d, 2 H), 7. 25-7. 35 ppm (d , 2H), 7.60-7.80 ppm (m, 8 H), 7.85-8.00 ppm (m, 4 H)

Example 3 Synthesis of Compound A-6

(3-1) Synthesis of Intermediate 3 In a 200 mL three-necked flask, 2.0 g of 4,4′-dichlorobenzophenone under a nitrogen stream, 4.4 g of 3-hydroxymethyl-4-methoxyphenylboronic acid, 1,4 40 mL of dioxane and 40 mL of saturated aqueous sodium hydrogen carbonate solution were added, and stirred at room temperature for 30 minutes. Thereafter, 0.2 g of bis (di-t-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) [(AMPHOS) ₂ PdCl ₂ ] was added, and the reaction was carried out at 90 ° C. for 3 hours. After confirming the progress of the reaction by TLC (thin layer chromatography), the reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by filtration. The obtained crude crystals were stirred in methanol and washed to obtain 3.5 g of Intermediate 3.

(3-2) Synthesis of Intermediate 4 In a 200 mL three-necked flask, 3.3 g of Intermediate 3 and 60 mL of tetrahydrofuran (THF) were charged under a nitrogen stream, and stirred in an ice bath for 10 minutes. To this was added 7.0 g of phosphorus tribromide (PBr ₃ ), allowed to react at room temperature for 4 hours, and then a small amount of water was added to stop the reaction. The precipitated crude crystals were collected by filtration and washed with methanol and ethyl acetate to obtain 3.5 g of Intermediate 4.

(3-3) Synthesis of Intermediate 5 In a 200 mL three-necked flask, 40 mL of tetrahydrofuran (THF) and 0.56 g of sodium hydride (NaH) (oil, 60%) were added, and after cooling in an ice bath, 2 3 mL of a tetrahydrofuran solution of 1.6 g of methyl-1,3-propanediol was added and stirred at room temperature. After 1 hour, 2.5 g of Intermediate 4 was added, and the reaction was performed at 60 ° C. for 3 hours. After cooling to room temperature, the reaction mixture was diluted with ethyl acetate, washed with water and saturated brine, and the organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, hexane was added to the filtrate, and recrystallization was performed to obtain 2.3 g of Intermediate 5.

(3-4) Synthesis of Compound A-6 In a 100 mL three-necked flask, 1.8 g of Intermediate 5, 10 mg of p-methoxyphenol (MEHQ), 20 mL of chloroform and 3.0 mL of triethylamine (TEA) are added, and ice is added Stir in the bath for 10 minutes. After 2.0 g of methacrylic acid chloride was added thereto and allowed to react at room temperature for 4 hours, a small amount of water was added to stop the reaction. The reaction mixture was diluted with ethyl acetate, washed with water and saturated brine, and the organic layer was dried over magnesium sulfate. After magnesium sulfate was removed by filtration, the residue was purified by silica gel column chromatography using hexane / ethyl acetate as a developing solvent to obtain 1.3 g of compound A-6. The ¹ H-NMR (Nuclear Magnetic Resonance) data of Compound A-6 were as follows.
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 0.92 to 1.00 (d, 6 H), 1.85 (s, 6 H), 2.10 to 2.20 ppm (m, 2 H); 40-3.50 ppm (m, 4 H), 3.85 ppm (s, 6 H), 4.00-4. 20 ppm (m, 4 H), 4.55 ppm (s, 4 H), 5. 60 ppm (s, 2 H) 6.00 ppm (s, 2 H), 7.10-7.20 ppm (d, 2 H), 7.65-7. 75 ppm (m, 4 H), 7. 8-7. 90 ppm (m, 8 H)

Example 4 Synthesis of Compound A-17

(4-1) Synthesis of Intermediate 6 40 g of hydroxypropyl acrylate, 300 mL of dichloromethane, 3.8 g of N, N-dimethylaminopyridine, 33.8 g of succinic anhydride, 2,6-di-t-butyl-4-methyl 200 mg of phenol were mixed and the internal temperature was heated to 40.degree. After stirring for 12 hours, the reaction solution was cooled to room temperature, 300 mL of water was added, the mixture was stirred for 1 hour, and liquid separation was performed. The collected organic layer was washed with 1 mol / L hydrochloric acid water and saturated brine and then dried over anhydrous sodium sulfate. The sodium sulfate was filtered off and the solvent was removed on a rotary evaporator to give 70 g of Intermediate 6 which is a clear oil.

(4-2) Synthesis of Compound 17 In a 300 mL three-necked flask, 9.1 g of Intermediate 3, 11.1 g of Intermediate 6, 240 mg of N, N-dimethylaminopyridine (DMAP) and 100 mL of dichloromethane were added, and an ice bath was added. The mixture was stirred for 10 minutes. To this was added 9.2 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDAC.HCl), and allowed to react at room temperature for 4 hours. The reaction mixture was diluted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine in this order, and the organic layer was dried over magnesium sulfate. After magnesium sulfate was removed by filtration, the residue was purified by silica gel column chromatography using hexane / ethyl acetate as a developing solvent to obtain 15.0 g of compound A-17. The ¹ H-NMR (Nuclear Magnetic Resonance) data of Compound A-17 were as follows.
¹ H-NMR (300 MHz, DMSO-d ₆ ): δ 1.10-1.20 (d, 6 H), 2.56-2.68 ppm (m, 8 H), 3.88 ppm (s, 6 H), 4. 00-4.20 ppm (m, 4 H), 5.00-5. 10 ppm (m, 2 H), 5. 15 ppm (s, 4 H), 5. 88-5. 96 ppm (m, 2 H), 6.05- 6.20 ppm (m, 2 H), 6.25-6. 35 ppm (m, 2 H), 7.15-7. 25 ppm (d, 2 H), 7. 7-7. 80 ppm (m, 4 H), 7. 80-7.90 ppm (m, 8 H)

(Comparative example 1)
A compound having the following structure was synthesized by the method described in JP-A-2014-43565. This was taken as comparative compound 1.

Evaluation of Refractive Index Properties of Compounds The compounds obtained in Examples 1 to 4 and Comparative Example 1 were dissolved in propylene glycol monomethyl ether acetate. At this time, the concentration of each compound was adjusted to be in the range of 1 to 10 weight percent. Each solution thus obtained was applied onto a quartz substrate by spin coating and dried on a hot plate at 80 ° C. for 3 hours to produce a substrate for evaluating optical characteristics having a layer having a thickness of 200 to 500 nm. This evaluation substrate is processed into a V-shape, and the refractive index (nF), Abbe number (dd) and partial dispersion ratio (θg, F) of each sample are measured by a Carnew precision refractometer (manufactured by Shimadzu Corporation, model number) It measured using KPR-2000). The measurement was performed three times for each sample, and the average value was taken as the measurement result. The results are shown in Table 1.

Thermosetting of a curable composition, refractive index property evaluation of a thermally cured product, and wet heat durability evaluation (Examples 5 to 8, Comparative Example 2) Preparation of a curable composition and thermal curing The composition shown in Table 2 Each component was added as such, and stirred to be uniform to prepare a curable composition. The resulting curable composition was poured into a transparent glass mold having a diameter of 20 mm and a thickness of 2 mm, and was heated to 200 ° C. in an atmosphere with an oxygen concentration of 1% or less to produce a thermally cured product. In order to evaluate the characteristics, it was processed into a V-shape, and the refractive index (nF), Abbe number (dd) and partial dispersion ratio (θg, F) of each sample were measured by the same method as in Examples 1-4. Moreover, the wet heat durability evaluation of each sample was also performed according to the following method. The results are shown in Table 2.

<Damp heat durability evaluation>
Each sample whose refractive index (nd) was measured was put in a thermo-hygrostatic chamber kept at 85 ° C. and 85% relative humidity and stored for 24 hours, and then taken out. Next, after standing at 25 ° C. and relative humidity 60% for 1 hour, the refractive index (nd) was measured, and the change amount of the refractive index before and after the wet heat test was evaluated in three stages of A to C below.
A: Refractive index change is 0.0005 or less before and after wet heat test B: Refractive index change is larger than 0.0005 and less than 0.001 before and after wet heat test C: Refractive index change is larger than 0.001 before and after wet heat test

The compounding quantity of each component described in Table 2 is represented by mass%. The details of the photopolymerization initiator and the thermal polymerization initiator described in Table 2 are as follows.
Irgacure 819 (manufactured by BASF)
Bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide Perbutyl O (manufactured by NOF Corporation)
t-Butylperoxy 2-ethylhexanoate Park Mill H-80 (manufactured by NOF Corporation)
Cumene hydroperoxide

As shown in Table 1, Examples 1 to 4 are preferable because the refractive index (nF) is equal to or higher than that of Comparative Example 1, the Abbe number (高 く d) is low, and the partial dispersion ratio (θg, F) is high. It was confirmed to have the characteristics.
As shown in Table 2, in Examples 5 to 8, it was confirmed that the wet heat durability was remarkably improved as compared with Comparative Example 2. Further, in comparison between Examples 7 and 8 and Comparative Example 2 in which the amount of copolymerized monomer is the same, Examples 7 and 8 have equal or higher refractive index (nF) and lower Abbe number (νd), It was confirmed that the partial dispersion ratio (θg, F) is high and that it has desirable characteristics.

Production of Lens (Example 9) Production of Composite Lens 200 mg of the curable composition obtained in Example 7 in a mold having a surface treated with chromium nitride (the surface in contact with the curable composition has an aspheric shape) A transparent glass lens (glass material BK-7, diameter 33 mm, center thickness 3 mm, surface in contact with the curable composition) so as to cover all the surfaces of the curable composition on the side not in contact with the molding die. A convex lens having a radius of curvature of 44.3 mm and a radius of curvature of the surface not in contact with the curable composition of 330.9 mm was placed on the surface, and the curable composition was spread so as to have a diameter of 30 mm. After this state, a 300 mJ / cm ² ultraviolet ray was irradiated from above the glass lens using Execure 3000 (manufactured by HOYA Co., Ltd.) to semi-cure the curable composition. Next, while maintaining a state of being sandwiched between the molding die and the glass lens, the temperature was raised to 200 ° C. while applying a pressure of 0.196 MPa (2 kgf / cm ² ) to the curable composition, and the composition was further cured. Then, the mold temperature was cooled to 180 ° C., and the cured product of the curable composition and the mold were pulled apart at a speed of 0.05 mm / sec to produce a composite lens.

Claims (17)

1. Curable composition containing the compound represented by following General formula (1).
   

   

   In the general formula (1),
   R ¹ to R ¹⁰ each independently represent a hydrogen atom or a substituent,
   At least one of R ¹ to R ⁵ is an aryl group substituted with a (meth) acryloyloxy group-containing substituent or a heteroaryl group substituted with a (meth) acryloyloxy group-containing substituent,
   At least one of R ⁶ to R ¹⁰ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
   R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ¹⁰ respectively They may be bonded to each other to form a linking group necessary to form a cyclic structure. However, the molecule represented by the general formula (1) does not include a polycyclic structure in which three or more aromatic rings are condensed.
2. At least one of R ⁶ to R ¹⁰ is an aryl group substituted with a substituent containing a (meth) acryloyloxy group, or a heteroaryl group substituted with a substituent containing a (meth) acryloyloxy group The curable composition according to Item 1.
3. The curable composition according to claim 1, wherein the compound is represented by the following general formula (2).
   

   

   In the general formula (2),
   R ^a and R ^b each independently represent a substituent other than an aryl group and a heteroaryl group,
   n1 and n2 each independently represent an integer of 0 to 4. When n1 is 2 or more, plural ^Ras may be the same or different, and when n2 is 2 or more, The plurality of R ^b may be the same or different,
   R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent,
   At least one of R ¹¹ to R ¹⁵ is a substituent containing a (meth) acryloyloxy group.
   R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , benzene ring Two R ^a each bonded to an adjacent ring skeleton-forming atom and two R ^b each bonded to an adjacent ring skeleton-forming atom of ^a benzene ring to each other to form a cyclic structure It may form a linking group. However, the molecule represented by the general formula (2) does not include a polycyclic structure in which three or more aromatic rings are condensed.
4. The curable composition according to claim 1, wherein the compound is represented by the following general formula (3).
   

   

   In the general formula (3),
   R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent other than an aryl group and a heteroaryl group,
   R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent,
   At least one of R ¹¹ to R ¹⁵ is a substituent containing a (meth) acryloyloxy group.
   R ¹ and R ² , R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ And R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ may be bonded to each other to form a linking group necessary to form a cyclic structure. However, the molecule represented by the general formula (3) does not include a polycyclic structure in which three or more aromatic rings are condensed.
5. R ¹² is a substituent containing a (meth) acryloyloxy group, the curable composition according to claim 3 or 4.
6. The curable composition according to any one of claims 3 to 5, wherein at least one of R ¹⁶ to R ²⁰ is a substituent containing a (meth) acryloyloxy group.
7. The curable composition according to any one of claims 3 to 6, wherein R ¹¹ , R ¹⁵ , R ¹⁶ and R ²⁰ are a hydrogen atom.
8. The curable composition according to any one of claims 1 to 7, wherein the substituent containing a (meth) acryloyloxy group is represented by the following general formula (4).
   

   

   In the general formula (4),
   Ac represents a (meth) acryloyloxy group,
   L ¹ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent,
   L ² represents a carbonyl group, an ether group, a thiocarbonyl group, a thioether group, or a linking group combining these groups,
   L ³ represents an alkylene group having 1 to 6 carbon atoms which may have a substituent,
   m1 represents an integer of 0 to 10, and when m1 is 2 or more, a plurality of L ^{1 s} may be the same or different, and a plurality of L ^{2 s} may be the same or different May be
   m2 represents 0 or 1;
   * Represents a bonding site of a substituent containing a (meth) acryloyloxy group.
9. The substituent containing the (meth) acryloyloxy group is a (meth) acryloyloxyalkoxy group, a (meth) acryloyloxyalkoxyalkyl group, a (meth) acryloyloxyalkoxycarbonylalkyl group, a (meth) acryloyloxyalkoxycarbonylacyloxy group, Alternatively, the curable composition according to claim 8, which is a (meth) acryloyloxyalkoxycarbonylacyloxyalkyl group.
10. The curable composition according to any one of claims 1 to 9, wherein the compound contains two or more substituents containing the (meth) acryloyloxy group in the molecule.
11. The curable composition according to any one of claims 1 to 10, wherein the compound does not contain a polycyclic structure in which two or more aromatic rings are condensed in the molecule.
12. The curable composition according to any one of claims 1 to 11, wherein the curable composition contains at least one selected from a photo radical polymerization initiator and a thermal radical polymerization initiator.
13. A semi-cured product of the curable composition according to any one of claims 1 to 12.
14. A cured product of the curable composition according to any one of claims 1 to 12.
15. An optical member comprising the cured product according to claim 14.
16. A lens comprising the cured product according to claim 14.
17. The compound represented by following General formula (2).
    

    

    In the general formula (2),
    R ^a and R ^b each independently represent a substituent other than an aryl group and a heteroaryl group,
    n1 and n2 each independently represent an integer of 0 to 4;
    R ¹¹ to R ²⁰ each independently represent a hydrogen atom or a substituent,
    At least one of R ¹¹ to R ¹⁵ is a substituent containing a (meth) acryloyloxy group.
    R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , benzene ring Two R ^a each bonded to an adjacent ring skeleton-forming atom and two R ^b each bonded to an adjacent ring skeleton-forming atom of ^a benzene ring to each other to form a cyclic structure It may form a linking group. However, the molecule represented by the general formula (2) does not include a polycyclic structure in which three or more aromatic rings are condensed.